DE102017126365A1 - Apparatus and method for producing a zeolite - Google Patents

Abstract

The invention relates to a device (PR) for the detemification of a zeolite, in particular for the production of nano- and / or microscale or nano- and / or microcrystalline detemplated zeolite particles (P), for example having an average particle size of 10 nm to a few millimeters, comprising at least one raw material material (RM) comprising a templated zeolite
at least one burner (1) and a combustion chamber (2) adjoining the burner (1) for generating a pulsating hot gas flow (HGS),
a reaction space arrangement (5) adjoining the combustion chamber (2),
- A between the combustion chamber (2) and the reaction space arrangement (5) arranged task location (AO) for the task of raw material (RM).
The invention further relates to a method for the detemification of a zeolite.

Description

The invention relates to a device for the detemification of a zeolite, in particular for the production of finely divided, in particular nano- and / or microscale or nano- and / or microcrystalline detemplated zeolite particles.

The invention furthermore relates to a process for the deplating of a zeolite, in particular for the production of finely divided, in particular nano- and / or microscale or nano- and / or microcrystalline, detemplated zeolite particles.

Such zeolite particles typically have an average particle or grain size of 10 nm to a few millimeters.

Zeolites are crystalline aluminosilicates that are found in many modifications in nature, but can also be produced synthetically. That is, zeolites are framework silicates characterized by voids in the crystalline structure. The general chemical formula for zeolites is Me _{2 / n} O.Al ₂ O ₃ .xSiO ₂ .yH ₂ O, where Me stands for alkali metals or alkaline earth metals and n for their valency. Alkali and alkaline earth ions are needed to charge balance for the incorporation of the trivalent Al ³⁺ ion in the formed of tetravalent Si ⁴⁺ ions SiO ₂ lattice. Those are only loosely tied to the grid and can be easily exchanged. The ion exchange capacity is used technically, for example for water softening. If the alkali and alkaline earth ions are exchanged for protons, zeolites can also be used as solid Brønsted acids for z. B. acid-catalyzed reactions can be used.

Depending on the structure of the zeolites, these include cavities and windows of different sizes in one or more spatial directions. A porosity of the zeolites makes it possible to absorb and release gases and vapors in a size-selective manner.

In addition to the size-selective adsorption but also a polarity of great importance. This is largely determined by the aluminum content in the lattice and an associated formation of polar centers. Polar gas molecules, such as CO ₂ and H ₂ O, then adsorb preferentially and particularly strongly at these sites. Aluminum-rich zeolites are therefore particularly adsorption-selective and have hydrophilic properties.

By substitution of the framework ions (Si, Al) against z. As Ge, Ti, Sn, Se, Hg, etc. can also be modified zeolites, such as. For example, germanium-containing or titanium-containing (eg, titanium silicalite TS) zeolites can be synthesized. Full substitution of silicon and aluminum is called zeolite analogues. If the framework structure is completely or partially built up by aluminum and phosphorus ions, the known zeolite analogues of AlPOs and SAPOs are formed.

A variety of zeolites and zeolite analogues can only be synthesized using organic template molecules. Template molecules are structure-directing agents that support the arrangement of lattice building blocks during zeolite synthesis. Typical templates are often organic ammonium hydroxides and salts, such as tetrapropylammonium hydroxide (TPAOH), tetrapropylammonium bromide (TPABr), tetraethylammonium hydroxide (TEAOH) etc. but also substances such as crown ethers and morpholine. The templates remain in the zeolite cage after synthesis. If the cage is to be accessible, the templates must be removed (detemplating). This is usually done by pyrolysis and oxidation. The temperatures are chosen so that the thermal decomposition of the template is largely completed, but the zeolite is exposed to the least possible thermal stress. Frequently, temperatures between 400 ° C and 500 ° C are selected. As an aggregate tube furnaces are often used in the art. The heating of the zeolite material may alternatively be carried out by microwave treatment. Furthermore, gentle detemplation methods, such as the treatment with H ₂ O ₂ or ozone are known, but which are not used technically.

Finely divided zeolites are particularly interesting because atoms or molecules that are part of a surface have different electronic and chemical properties than their atoms or molecules inside the material. The smaller a particle is, the higher its content of surface atoms. Accordingly, very finely divided materials, especially nanoparticles, can have quite different mechanical, electronic, chemical or optical properties than larger, chemically and mineralogically identical particles, making them particularly interesting for specific applications. In addition, finely divided particles allow the production of particularly thin layers when deposited as a layer.

• - Chemische Herstellung in Lösungen (z.B. Sol-Gel-Methode, hydrothermale Synthese etc.);
• - Herstellung im Plasma oder Herstellung aus der Gasphase (Aerosolprozess).

For the production of finely divided powders, essentially the following production processes have been established:

• - Chemical preparation in solutions (eg sol-gel method, hydrothermal synthesis, etc.);
• - Production in plasma or production from the gas phase (aerosol process).

Depending on the field of application of the nanoparticles, a well-defined and narrow particle size distribution is usually required. Depends on the chemical nature of the desired nanoparticles, one or the other method is better suited to achieve a good result. In most cases, solution or self-assembly methods provide the best results, but are difficult or impossible to do on a large scale.

From WO 02/072471 or from the DE 10 2004 044 266 A1 pulsation reactors for the production of finely divided powders are known.

The invention is based on the object to provide an improved apparatus and an improved method for the detemination of a zeolite, in particular for the production of finely divided, for example nano- and / or micro-scale or nano- and / or microcrystalline detemplated zeolite particles.

With regard to the device, the object is achieved by the features specified in claim 1 and in terms of the method by the features specified in claim 6.

Advantageous embodiments of the invention are the subject of the dependent claims.

The device according to the invention for the detemification of a zeolite, in particular for the production of nano- and / or microscale or nano- and / or microcrystalline detemplated zeolite particles, for example having an average particle size of 10 nm to a few millimeters, comprising at least one templathaltigen zeolite Raw material material includes at least one burner and a combustion chamber adjoining the burner for generating a pulsating hot gas flow. The combustion chamber is adjoined by a reaction space arrangement, wherein a task location for discharging the raw material material is arranged between the combustion chamber and the reaction space arrangement.

Nanoscale particles which are produced in the apparatus described above are in particular nanoscale particles according to DIN SPEC 1121 (DIN ISO / TS 27687) which, for example, have particle sizes in the range from 10 nm to 120 nm, in particular in the range from 20 nm to 100 nm, for example from 40 nm to 80 nm. Nanocrystalline particles which are produced in the device described above are in particular understood to mean particles whose grain is formed from a plurality of small crystals and have a particle size of a few millimeters, in particular less than 8 mm, in particular less than 5 mm or 3 mm, respectively. Also, finely divided particles may be understood to mean nanocrystalline particles having a particle size of <20 μm. In addition, it can be understood that nanoparticles, in particular so-called nanoscale particles, are based on particle sizes in the nanoscale, with nanocrystalline particles having a comparatively larger particle size. The nanocrystalline particles are characterized by, for example, a polycrystalline structure in which the crystals can have size arrangements in the nanoscale. These substances can also have differentiated properties. In particular, both types of particles can be generated depending on the input material.

The raw material material is given up, for example, in the form of a solid, a solution or suspension. The task of the raw material can be done depending on the design at different places.

The reaction space is understood to be, in particular, that plant or reactor space volume, such as, for example, pipe, container and / or pipe volume, from the point of application of the raw material to cooling of the material prior to separation or filtering of the produced particles.

Using conventional prior art devices, performing zeolite detemplation, ie, removing zeolite templates, is very expensive and must be performed in several separate operations and associated breaks. In particular, said processes have limitations if particularly finely divided zeolites, in particular zeolite nanoparticles, are to be detembled. These limitations relate, for example, to discharging the fine particles from a hot zone, for example in a tube furnace, insufficient flow of powdered beds, for example in a muffle furnace and / or H ₂ O ₂ or ozone treatment, an insufficient penetration depth in powder beds, for example Use of a microwave. Another challenge is the occurrence of sudden combustion reactions and the associated formation of hot zones, so-called hot spots. A probability of hot spots increases with reducing particle diameter. The excessive temperatures occurring in the hot spots lead to the destruction of zeolite nanoparticles and their aggregation and thus to a loss of the nanoparticulate character.

In a particularly surprising manner, the detemplation of the zeolite can be carried out continuously in a single operation within the apparatus according to the invention due to their mode of operation as a pulsation reactor. Due to the use of Pulsationsreaktors is opposite From the prior art known devices, such as a rotary kiln, advantageously a treatment of individual particles, ie the individual particles possible. Here, process temperatures of more than 500 ° C are possible without causing damage to the zeolite. Furthermore, in contrast to a known from the prior art detemplation in a microwave, a rotary kiln or a muffle furnace, in which occurs a sudden combustion and decomposition of the template, due to the use of Pulsationsreaktors formation of so-called hot spots and damage to the crystalline structure of the zeolite avoided by leaking gases. This results in particular from a relatively short residence time of the zeolite in the device and thereby taking place in a short time heating and cooling. Due to the pulsation of the hot gas flow in this case a particularly high mass and heat transport is achieved, due to which the damage to the zeolite is avoided. At the same time, however, complete combustion of the at least one template takes place. Thus, the depletion of the zeolite is complete and very fast, easy and reliable feasible. A micro- or nanocrystalline character of the zeolite is maintained in an advantageous manner.

In this case, in the case of detemplation, in particular annealing losses of less than 10% by weight, a carbon content in the detemplated zeolite of less than 0.1% by weight, while maintaining the crystal structure of the zeolite, are realized.

According to one possible embodiment of the device, the reaction space arrangement comprises a reaction space designed as a resonance pipe. For example, the resonance tube comprises a circular cross-section, which in particular a uniform atomization of the material to be supplied in the hot gas stream and a particularly uniform temperature distribution over the cross section can be made possible.

In an alternative or additional embodiment of the device, the combustion chamber is designed as a combustion chamber whose dimensions, in particular its diameter, is greater than dimensions, in particular the diameter of the resonance tube. When selecting certain geometries of the combustion chamber and the reaction space, in particular the resonance tube, the pulsations of the hot gas stream can be amplified.

According to another possible embodiment of the device, the reaction space arrangement comprises a further reaction space, which is connected downstream of the reaction space. This further reaction space allows a prolonged residence time of the hot gas stream with the zeolite in the reaction space arrangement and thus complete detemplation. The two reaction spaces can form a uniform reaction space.

For the separation of the particles as a reaction product, d. H. of the particulate detemplated zeolite, according to a possible development of the device of the reaction space arrangement, a suitable separation device for finely divided particles or ultrafine particles is connected downstream of the hot gas stream.

In one possible embodiment of the device, it is provided that the separation device is followed by an exhaust gas aftertreatment, which comprises, for example, at least one scrubber and at least one blower, by means of which a purification of an emerging exhaust gas can be realized.

In the method according to the invention for the detemification of a zeolite, in particular for the production of nano- and / or microscale or nano- and / or microcrystalline detemplated zeolite particles, for example having an average particle size of 10 nm to a few millimeters, of at least one templated zeolite comprehensive raw material material by means of the device according to the invention or embodiments thereof, the raw material is supplied at the point of delivery of a flame generated by the burner such that forms a raw material leading hot gas stream. The raw material is thermally treated in the hot gas stream in the reaction space arrangement such that at least one template is at least partially removed from the templated zeolite. After flowing through the reaction space arrangement, the detemplated zeolite is separated from the hot gas stream.

In a particularly surprising manner, the detemplation of the zeolite by means of the method can be carried out continuously in a single operation due to the functioning of the device as a pulsation reactor. Here, process temperatures of more than 500 ° C are possible without causing damage to the zeolite. Furthermore, in contrast to a known from the prior art detemplation in a microwave, a rotary kiln or a muffle furnace, in which occurs a sudden combustion and decomposition of the template, due to the use of Pulsationsreaktors formation of so-called hot spots and damage to the crystalline structure of the zeolite avoided by leaking gases. This results in particular from a relatively short residence time of the zeolite in the device and the heating taking place in a short time and cooling off. Due to the pulsation of the hot gas flow in this case a particularly high mass and heat transport is achieved, due to which the damage to the zeolite is avoided. At the same time, however, complete combustion of the at least one template takes place. Thus, the depletion of the zeolite is complete and very fast, easy and reliable. A micro- or nanocrystalline character of the zeolite is maintained in an advantageous manner.

In this case, in the case of detemplation, in particular annealing losses of less than 10% by weight, a carbon content in the detemplated zeolite of less than 0.1% by weight, while maintaining the crystal structure of the zeolite, are realized.

According to a possible embodiment of the method, the hot gas stream with the raw material material is passed through a reaction space designed as a resonance tube and another reaction space, which is connected downstream of the reaction space, and thermally treated. For example, the resonance tube comprises a circular cross-section, which in particular a uniform atomization of the material to be supplied in the hot gas stream and a particularly uniform temperature distribution over the cross section can be made possible. Due to the treatment of the zeolite in multiple reaction spaces, a prolonged residence time of the hot gas stream with the zeolite in the reaction space arrangement is achieved and thus a complete detemplation is performed.

According to another possible embodiment of the method, the templated zeolite in powder form or the templated zeolite in a suspension with water is used as raw material.

According to a possible development of the method, a process temperature in the range from 500 ° C. to 900 ° C., for example from 600 ° C. to 900 ° C., for example from 700 ° C. to 900 ° C., for example from 700 ° C. to 800 ° C., is used in the reaction space arrangement ° C, set. The setting of the process temperature is carried out for example by adjusting an air / fuel mixture at the entrance of the burner, the process temperature is chosen in particular such that the detemplation is complete and damage to the zeolite is avoided.

A possible embodiment of the process envisages using as template-containing zeolite a silicalite which comprises tetrapropylammonium hydroxide and / or tetrapropylammonium bromide as template. Another possible embodiment of the method provides that the hot gas stream is cooled with the detemplated zeolite after flowing through the reaction space arrangement and then the separation device for separating the zeolite from the hot gas stream is supplied. Thus, the detemplated zeolite can be deposited as finely divided particles or Feinstpartikel.

A possible development of the method provides that the hot gas stream is supplied after the separation of a cleaning. Thus, a purification of a generated exhaust gas can be realized.

According to one possible embodiment of the method, the detemplated zeolite in the hot gas stream is thermally treated in the apparatus so that a surface modifier also supplied to the hot gas stream attaches to the zeolite, and after flowing through the reaction space arrangement, the surface-modified zeolite is separated from the hot gas stream. An object of the surface modifier takes place, for example, in the further reaction space. The task can be done by means of atomization.

In a particularly surprising manner, the surface modification of the zeolite can be carried out in a single operation within the device due to their operation as a pulsation reactor. In this case, process temperatures of more than 500 ° C are possible without causing damage to the surface modifier or burning the same. This results in particular from a relatively short residence time of the zeolite and the surface modifier in the device and thereby taking place in a short time heating and cooling. Due to the pulsation of the hot gas flow in this case a particularly high mass and heat transport is achieved, due to which the damage and the burning of the surface modifier are avoided. Thus, the surface modification of the zeolite by the method can be carried out particularly quickly, easily and reliably.

For example, the method and apparatus allow for successful modification of surface properties of detemplated zeolites by applying and attaching polysilanes, polysilazanes, and similar organometallic compounds of limited thermal stability despite relatively high process temperatures.

In order to perform the surface modification of the zeolite in a single operation within the device particularly quickly, easily and reliably, in a possible development of the method in the region of the device in which the surface modification takes place, a Process temperature of 500 ° C to 850 ° C, for example, from 550 ° C to 700 ° C, for example, from 580 ° C to 670 ° C, adjusted. The setting of the process temperature is carried out for example by adjusting an air / fuel mixture at the entrance of the burner, wherein the process temperature is chosen in particular such that the solvent burns as completely as possible, no deflagrations take place and the surface modifier is not damaged or burned.

The surface modification can be carried out within the device from a liquid and / or from a gas phase of the raw material.

In order to achieve a hydrophobing of the outer surface of the zeolite, for example of the silicalite, is used according to a possible development of the method as a surface modifier 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane.

According to another possible embodiment of the method, the hot gas stream is cooled with the surface-modified zeolite and then fed to the separation device for separating the surface-modified zeolite from the hot gas stream. Thus, the surface-modified zeolite can be deposited as finely divided particles or Feinstpartikel.

Embodiments of the invention are explained in more detail below with reference to drawings.

• 1 schematisch ein erstes Ausführungsbeispiel einer Vorrichtung zur Herstellung von Partikeln,
• 2 schematisch ein zweites Ausführungsbeispiel einer Vorrichtung zur Herstellung von Partikeln und
• 3 schematisch ein drittes Ausführungsbeispiel einer Vorrichtung zur Herstellung von Partikeln.

Show:

• 1 schematically a first embodiment of a device for producing particles,
• 2 schematically a second embodiment of an apparatus for producing particles and
• 3 schematically a third embodiment of an apparatus for producing particles.

Corresponding parts are provided in all figures with the same reference numerals.

1 shows a possible first embodiment of a device PR , in particular a thermal reactor for the production of finely divided particles P , in particular of nano- and / or microcrystalline particles P , For example, they have at least one raw material RM produced particles P in the final product a nano- and / or microcrystalline structure and / or a nano- and / or microscale structure with an average particle size of 10 nm to a few millimeters.

The device PR is used for a detemplation of a templated zeolite, ie for the removal of templates from a zeolite. That is, the raw material RM comprises at least one templated zeolite, for example a silicalite, which comprises as a template tetrapropylammonium hydroxide and / or tetrapropylammonium bromide.

The thermal reactor is exemplified as a pulsation reactor, in which in a pulsating, oscillating hot gas stream HGS the particles P be formed. For this purpose, the thermal reactor comprises a burner 1 and one to the burner 1 subsequent combustion chamber 2 for generating the pulsating hot gas flow HGS , This will be combustion gases VG and at least one fuel BS via a feeder 3 together or separately in the burner 1 and over this into the combustion chamber 2 brought in.

As fuel BS In particular, a combustible gas, such as natural gas and / or hydrogen, is supplied. Also, another suitable gas may be supplied as fuel gas.

As combustion gas VG For example, ambient air, oxygen, etc. are used. The supplied combustion gases VG and fuels BS for example, in the combustion chamber 2 ignited. The resulting flame pulsates due to a self-excited periodic-transient combustion and generates a pulsating hot gas flow HGS in the combustion chamber 2 , The pulsating hot gas flow HGS flows from the combustion chamber 2 flow outlet side in a reaction space arrangement 5 , which in the illustrated embodiment, for example, designed as a resonance tube reaction space 5.1 and a downstream of this further reaction space 5.2 includes. In this case, the two reaction spaces 5.1 and 5.2 form a single reaction space. A device section PR ' indicates a region of the device PR which is different from the feeder 3 until at least the end of the formed as a resonance tube reaction space 5.1 extends.

In detail, the fuel BS as well as the necessary combustion gas VG together (premixed in an upstream mixing chamber) or separated over the burner 1 the combustion chamber 2 fed and ignited there. The fuel burns BS and the combustion gas VG very fast and create a pressure wave in the direction of the reaction space 5.1 , For example, in the direction of the resonance tube. Due to the lower flow resistance in the direction of the reaction space 5.1 the propagation of a pressure wave occurs. During the acoustic Vibration curve is the pressure in the combustion chamber 2 reduced, so that new fuel gas mixture or new fuel BS and combustion gas VG can flow or can. This process of the subsequent flow through pressure fluctuations takes place automatically and periodically. The pulsating combustion process in the combustion chamber 2 generates the pulsating hot gas flow HGS , which is characterized by a high degree of turbulence. The high flow turbulence and the constantly changing flow velocity prevent the build-up of an insulating gas envelope (boundary layer) around the raw material material RM , in particular a raw material mixture, forming particles P , whereby a higher heat transfer and mass transfer (between raw material and hot gas), that is a faster reaction at relatively lower temperatures, is possible. Typically, the residence time is less than one second to a few seconds. In addition, a particularly large proportion of the particles formed reaches P a desired spherical shape. For the separation of the particles P as a reaction product from the hot gas stream HGS joins the reaction space arrangement 5 a suitable separation device 7 for finely divided particles P or finest particles.

The frequency of the pulsating hot gas flow HGS is in the Hertz range, in particular in a range of a few hertz, for example greater than 5 Hz, in particular greater than 50 Hz, for example in a range of 5 Hz to 350 Hz. Parameters of the hot gas flow HGS , such as amplitude and / or frequency of the vibration, are adjustable. This can be based on the combustion parameters such as fuel quantity, air quantity, air temperature, fuel temperature and / or flame temperature, location of the fuel / air application and / or on proportions and / or changes of these combustion chamber 2 , Burner 1 and / or the reaction space arrangement 5 , in particular the reaction spaces 5.1 and 5.2 , respectively.

The reaction space 5.1 is formed, for example, as a resonance tube. The combustion chamber 2 is formed as a combustion chamber whose dimensions, in particular its diameter, is greater than the dimensions, in particular the diameter of the reaction space 5.1 ,

Between the combustion chamber 2 and the reaction space 5.1 is a job site AO arranged on which a task of raw material RM , hereinafter referred to as raw material task occurs. These are raw material materials RM in the form of solid, gaseous and / or liquid raw materials and / or mixtures of raw materials, introduced as raw material solution or raw material dispersion.

The task of the raw material RM thus takes place at the upper end of the combustion chamber 2 , in particular at the transition from the combustion chamber 2 to the reaction space arrangement 5 and outside the combustion chamber 2 , In particular, the task of raw material occurs RM in the hot gas stream HGS through a nozzle when the raw material RM is present as a suspension or solution.

For example, the task of raw material occurs RM as a suspension of the templated zeolite and water by means of a two-fluid nozzle. Here, a solids content of zeolite in the suspension, for example, 30%.

Alternatively, the task of raw material RM also in powder form.

In addition, the raw material material RM from the direction of the burner 1 into the combustion chamber 2 be introduced. Alternatively or additionally, the raw material RM also in the adjoining arranged reaction space 5.1 , in particular in the resonance tube, are introduced.

For this purpose, the device PR further not shown task locations in the combustion chamber 2 , in particular at the flow inlet-side end, and / or along the reaction space 5 respectively.

In one possible development, a task location is in the area of the burner 1 , in particular at the output of the burner 1 , arranged that the raw material RM at the flow inlet end of the combustion chamber 2 is introduced. As a result, a substantially high temperature gradient can be generated, whereby the raw material material RM heats up faster. In particular, a heating rate can be achieved by arranging this task location in the area of the burner 1 and at the flow inlet end of the combustion chamber 2 increase. Furthermore, sticking and sticking of the substance by means of spraying the raw material material RM , For example, in the form of a liquid, as far as possible prevented in an open space.

Thus, also the combustion chamber 2 even form a reaction space. Generally takes place in the combustion chamber 2 the combustion takes place and the generation of the pulsating hot gas flow HGS , In contrast, takes place in the reaction space arrangement 5 usually no combustion of the fuel BS more instead. But it is also possible, especially at the entrance of the reaction space 5.1 and thus in the region of the upper end of the combustion chamber 2 additional fuel BS and / or combustion gas VG as an intermediate firing supply. It is also possible to enter the combustion chamber 2 Raw material material RM via the optional task location in the area of the burner 1 , in particular at the output of the burner 1 to feed. In this case, the combustion chamber forms 2 also a reaction space, since there is also treated material.

The reaction space arrangement 5 is the separator 7 downstream. The raw material RM is by means of the hot gas flow HGS from the at least one material task via the reaction space arrangement 5 forming the particles P to the separation device 7 guided and transported. The separation device 7 is for example a cyclone separator or a filter, in particular a hot gas filter. From the separator 7 become the manufactured particles P deposited.

Due to the combustion in the reaction space arrangement 5 outflowing hot gas stream HGS becomes a negative pressure in the combustion chamber 2 generates and thus reduces the pressure, so that inflowing combustion gases VG and / or fuels BS light yourself. This process of the subsequent flow by pressure and negative pressure is self-regulating periodically. The pulsating combustion process in the combustion chamber 2 continues with the propagation of a pressure wave in the reaction space arrangement 5 and thus in the reaction spaces 5.1 . 5.2 Energy free and stimulates an acoustic vibration there.

In the hot gas stream HGS the particle treatment takes place. The generated hot gas stream HGS preferably has a combustion frequency of 5 Hz to 350 Hz. A process temperature is set, for example, in the range of 500 ° C to 900 ° C, for example, from 600 ° C to 900 ° C, for example, from 700 ° C to 900 ° C, for example, from 700 ° C to 800 ° C.

For setting and monitoring the process temperature are at different positions on the device PR Pressures, temperatures and flow rates as well as operating parameters of components of the device PR measured.

Within the reaction space arrangement 5 become the template contained in the zeolite particles within the hot gas stream HGS burned, due to the reaction chamber designed as a resonance tube 5.1 downstream further reaction space 5.2 a residence time of the zeolite in the hot gas stream HGS is extended. As a result, a complete combustion of the template can be achieved in a simple manner. Furthermore, in the case of detemplation, in particular incandescence losses of less than 10% by weight and a carbon content in the detemplated zeolite of less than 0.1% by weight are achieved while retaining the crystal structure of the zeolite.

Due to the short residence time of the zeolite in the hot gas stream HGS and the operation of the device designed as Pulsationsreaktor PR surprisingly, despite the process temperature in the range of 500 ° C to 900 ° C takes place no damage or combustion of the zeolite.

Subsequently, for example by means of cooling air, in particular filtered ambient air, the hot gas flow HGS and the particles in it P cooled. The in the hot gas stream HGS formed finely divided particles P then enter the separation device 7 attached to the reaction space arrangement 5 followed. In the separator 7 For example, the powder deposition takes place by the particles formed P , ie the detemplated zeolite, from the hot gas stream HGS be separated.

The separator 7 is an exhaust aftertreatment 8th downstream, by means of which a purification of a resulting exhaust gas A he follows. This is for example in the exhaust A present hydrogen bromide, short HBr, in the detemplation of a silicalite, which contains as a template tetrapropylammonium bromide, from the exhaust gas A away. The exhaust A is then, for example, a fireplace 9 returned to the environment.

In one possible embodiment, a surface modification of the detemplated zeolite of the device PR additionally a surface modifier before cooling the hot gas stream HGS and the particle P and the deposition of the same supplied. An object of the surface modifier takes place, for example, in the further reaction space 5.2 , The task can be done by means of atomization.

The surface modifier is, for example, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane.

Inside the hot gas stream HGS become the particles P and the surface modifier is thermally treated such that the surface modifier attaches to the zeolite and forms a particle P form surface-modified. For this purpose, in the area of the device PR in which the surface modification takes place, for example, a process temperature in the range of 500 ° C to 850 ° C, for example, from 550 ° C to 700 ° C, for example, from 580 ° C to 670 ° C, adjusted. The setting of the process temperature, for example, by adjusting an air / fuel mixture at the entrance of the burner 1 , wherein the process temperature is chosen in particular such that the Solvent burns as completely as possible, no deflagration take place and the surface modifier is not damaged or burned.

For setting and monitoring the process temperature are at different positions on the device PR Pressures, temperatures and flow rates as well as operating parameters of components of the device PR measured.

Due to the short residence time of the surface modifier in the hot gas stream HGS and the operation of the device designed as Pulsationsreaktor PR surprisingly, despite the process temperature in the range of 500 ° C to 850 ° C, no damage or combustion of the temperature-sensitive surface modifier takes place.

In the embodiment in which the zeolite is a silicalite and the surface modifier is 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, the product obtained is a particulate surface-modified zeolite which is hydrophobic and thus not or only partially soluble in water.

2 shows a second possible embodiment of the device PR for the production of particles P ,

This includes the exhaust aftertreatment 8th in addition to the in 1 illustrated first embodiment, at least one scrubber 8.1 and a fan 8.2 , The scrubber 8.1 is for example a liberation of the exhaust gas A of hydrogen bromide filled with sodium hydroxide.

In 3 a third possible embodiment of the device PR for the production of particles P shown.

Unlike the in 1 illustrated first embodiment includes the reaction space arrangement 5 only the reaction space designed as a resonance tube 5.1 , Thus, a shorter residence time of the zeolite and / or the surface modifier within the hot gas stream HGS will be realized.

LIST OF REFERENCE NUMBERS

1

burner

2

combustion chamber

3

feed

5

Reaction chamber arrangement

5.1

reaction chamber

5.2

reaction chamber

7

separating

8th

exhaust aftertreatment

8.1

washer

8.2

fan

9

fireplace

A

exhaust

AO

Aufgabeort

BS

fuel

HGS

Hot gas stream

P

particle

R

flow direction

PR

device

PR '

device section

RM

Raw material material

VG

combustion gas

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102004044266 A1 [0012]

Claims (14)

Device (PR) for the detemination of a zeolite, in particular for the production of nano- and / or microscale or nano- and / or microcrystalline detemplated zeolite particles (P), for example with an average particle size of 10 nm to a few millimeters, of at least one templated zeolite comprising raw material (RM), comprising at least one burner (1) and a combustion chamber (2) adjoining the burner (1) for generating a pulsating hot gas flow (HGS), a reaction space arrangement (5) adjoining the combustion chamber (2), - A between the combustion chamber (2) and the reaction space arrangement (5) arranged task location (AO) for the task of raw material (RM). Device after Claim 1 wherein the reaction space arrangement (5) comprises a reaction space (5.1) formed as a resonance pipe. Device after Claim 2 , wherein the reaction space arrangement (5) comprises a further reaction space (5.2), which is connected downstream of the reaction space (5.1). Device according to one of the preceding claims, wherein the reaction space arrangement (5) is followed by a separation device (7). Device after Claim 4 , wherein the separation device (7) an exhaust aftertreatment (8) is connected downstream. Process for the detemification of a zeolite, in particular for the production of nano- and / or microscale or nano- and / or microcrystalline detemplated zeolite particles (P), for example with an average particle size of 10 nm to a few millimeters, of at least one templated zeolite comprehensive raw material (RM) by means of a device (PR) according to one of the preceding claims, wherein the raw material (RM) at the point of application (AO) is supplied to a flame produced by the burner (1) in such a way that a hot gas stream (HGS) leading to the raw material (RM) forms, - The raw material (RM) in Hei0gasstrom (HGS) in the reaction space arrangement (5) is thermally treated such that at least one template is at least partially removed from the templathaltigen zeolite, and - After flowing through the reaction space arrangement (5) of the detemplated zeolite from the hot gas stream (HGS) is separated. Method according to Claim 6 , - wherein the hot gas stream (HGS) with the raw material (RM) through a designed as a resonance tube reaction space (5.1) and another reaction space (5.2), which is downstream of the reaction space (5.1), passed and thermally treated. Method according to Claim 6 or 7 , wherein as a raw material material (RM) - the templated zeolite in powder form or - the templated zeolite is used in a suspension with water. Method according to one of Claims 6 to 8th , wherein in the reaction space arrangement (5) a process temperature in the range of 500 ° C to 900 ° C is set. Method according to one of Claims 6 to 9 in which the templated zeolite used is a silicalite which comprises as template tetrapropylammonium hydroxide and / or tetrapropylammonium bromide. Method according to one of Claims 6 to 10 , wherein the hot gas stream (HGS) is cooled with the detemplated zeolite after flowing through the reaction space arrangement (5) and then the separation device (7) for separating the surface-modified zeolite from the hot gas stream (HGS) is supplied. Method according to Claim 11 , wherein the hot gas stream (HGS) is supplied after the separation of a cleaning. Method according to one of Claims 6 to 10 in which the detemplated zeolite present in the hot gas stream (HGS) is thermally treated in the device (PR) in such a way that a surface modifier also supplied to the hot gas stream (HGS) bonds to the zeolite, and - after flowing through the reaction space arrangement (5) surface-modified zeolite is separated from the hot gas stream (HGS). Method according to Claim 13 in which the hot gas stream (HGS) is cooled with the surface-modified zeolite and then fed to the separation device (7) for separating the surface-modified zeolite from the hot gas stream (HGS).

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